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Abstract:

Dielectric ceramics represented as: CaxZrO3+aMn+bLi+cB+dSi and
comprising: based on 100 mol of CaxZrO3 (where
1.00≦x≦1.10), 0.5≦a≦4.0 mol, and
6.0≦b+c+d≦15.0 mol, in which
0.15≦b/(c+d)≦0.55, and 0.20≦d/c≦3.30 or
multi-layer ceramic capacitor using the same.

5. Dielectric ceramics according to claim 1, wherein a portion of Ca in
the CaxZrO3 is replaced by Sr and further, Mg and/or Al is
contained.

6. Dielectric ceramics according to claim 1, wherein a portion of Zr in
the CaxZrO3 is replaced by Ti and, further, Mg and/or Al is
contained.

7. Dielectric ceramics according to claim 1, wherein a portion of Ca in
the CaxZrO3 is replaced by Sr and Ti, and, further, Mg and/or
Al is contained.

8. A multi-layer ceramic capacitor including a plurality of dielectric
ceramic layers, an internal electrode comprising Cu or a Cu alloy formed
between the dielectric ceramic layers, and an external electrode
connected electrically with the internal electrode, in which the
dielectric ceramic layer comprises the dielectric ceramics according to
claim 1.

Description:

BACKGROUND OF THE INVENTION

[0001]1. Field of the Invention

[0002]The present invention concerns dielectric ceramics comprising
CaZrO3 as a main ingredient and a multi-layer ceramic capacitor of
excellent life characteristics using the same and, more in particular, it
relates to dielectric ceramics used for a multi-layer ceramic capacitor
including an internal electrode comprising Cu or Cu alloy and a
multi-layer ceramic capacitor using the same.

[0003]2. Description of the Related Art

[0004]Heretofore, dielectric ceramics are used, for example, in dielectric
resonators, filters, or multi-layer capacitors. For the dielectric
ceramics used for the multi-layer capacitors, etc., it has been desired
that the temperature coefficient of static capacitance (permittivity) is
smaller along with increase in the working frequency of equipments in
recent years (about 100 MHz to 2 GHz). Further, for the characteristics
of the multi-layer capacitor used in high frequency circuits, it has been
demanded that ESR (equivalent series resistance) is lower and the loss in
the high frequency region is smaller (higher Q value). On the other hand,
in view of reduction for the cost, it is necessary to select a base metal
as an internal electrode of low specific resistivity. Accordingly, Cu is
used instead of Ni and Pd. Further, for dielectrics, those having high Q
value, small temperature coefficient of the permittivity and high
reliability are demanded. Further, since Cu is used for the internal
electrode, it has been demanded for the dielectrics that they can be
fired at a relatively low temperature of 1080° C. or lower and
they are non-reducing materials in order to prevent oxidation of Cu.
Further, with an environmental view point, dielectrics not containing Pb
or Bi are desired. Patent documents 1 and 2 disclose inventions
concerning dielectric ceramic compositions satisfying such demands and
further show the use of such dielectric ceramic compositions to
multi-layer ceramic capacitors.

[0005][Patent document 1] JP-A-5-217426

[0006][Patent document 2] JP-A-11-106259

[0007]The patent document 1 shows a non-reducing dielectric ceramic
composition containing
(Ca1-xSrx)m(Zr1-yTiy)O3-zMnO2-wSiO.sub-
.2 as a main ingredient, and
a(LiO1/2)--RO)-(1-a)(BO3/2--SiO2) (in which RO is at least
one member of SrO, BaO and CaO) as an additive. The non-reducing
dielectric ceramic composition "enables to obtain dielectric ceramics
that can be fired at a low temperature of about 1000° C. or lower,
can use copper as an electrode material, in addition, has a high Q value
and permittivity, and is also stable for the temperature characteristic
of the permittivity" (column [0005]). However, no sufficient study has
been made on the improvement of the life characteristic of the
multi-layer ceramic capacitor using Cu as the internal electrode.

[0008]The patent document 2 shows a dielectric ceramic composition
containing a composite oxide represented by
(CaO)x(Zr1-y.Tiy)O2, an Mn compound, and a glass
ingredient represented by (aLi2O-bB2O3-cCaO). The
dielectric ceramic composition "can be fired even in a reducing
atmosphere at 1000° C. or lower, has high permittivity, in
addition, is stable for the temperature characteristic of permittivity,
has a Q value as Qf in a high frequency region (GHz band) of 10000 or
more, with the Q value being remarkably improved particularly in the high
frequency region" (column 0015). However, no sufficient study has been
made on the improvement of the life characteristic of the multi-layer
ceramic capacitor using Cu as the internal electrode.

SUMMARY OF THE INVENTION

[0009]In a certain aspect of the invention, it is intended to solve at
least one of subjects not studied sufficiently in the techniques
described above and intended to improve the life characteristic of a
multi-layer ceramic capacitor using dielectric ceramics comprising
CaZrO3 as a main ingredient and using Cu as an internal electrode.

[0010]In another aspect of the invention, at least one of the following
means is adopted for solving one or more of the subjects described above.

(1) Dielectric ceramics represented as:

[0011]CaxZrO3+aMn+bLi+cB+dSi, comprising:

[0012]based on 100 mol of CaxZrO3 (where Ca includes a partial
substitute by Sr, etc., Zr includes a partial substitute by Ti, etc., and
1.00≦x≦1.10),

[0013]0.5≦a≦4.0 mol, and

[0014]6.0≦b+c+d≦15.0 mol, in which

[0015]0.15≦b/(c+d)≦0.55, and

[0016]0.20≦d/c≦3.30.

(2) Dielectric ceramics according to (1) above, wherein a portion of Ca in
the CaxZrO3 is substituted by Sr.(3) Dielectric ceramics
according to (1) or (2) above, wherein a portion of Zr in the
CaxZrO3 is substituted by Ti.

(4) Dielectric ceramics according to any one of (1) to (3) above, wherein
Mg and/or Al is further contained.(5) A multi-layer ceramic capacitor
including a plurality of dielectric ceramic layers, an internal electrode
comprising Cu or a Cu alloy formed between the dielectric ceramic layers,
and an external electrode connected electrically with the internal
electrode, wherein the dielectric ceramic layer comprises dielectric
ceramics according to any one of (1) to (4) described above.

[0018]Use of the dielectric ceramics based on the aspects disclosed here
in which the composition comprising CaZrO3 as the main ingredient is
specified provides an effect of improving the life characteristic of a
multi-layer ceramic capacitor using Cu as the internal electrode.

[0019]For purposes of summarizing aspects of the invention and the
advantages achieved over the related art, certain objects and advantages
of the invention are described in this disclosure. Of course, it is to be
understood that not necessarily all such objects or advantages may be
achieved in accordance with any particular embodiment of the invention.
Thus, for example, those skilled in the art will recognize that the
invention may be embodied or carried out in a manner that achieves or
optimizes one advantage or group of advantages as taught herein without
necessarily achieving other objects or advantages as may be taught or
suggested herein.

[0020]Further aspects, features and advantages of this invention will
become apparent from the detailed description of the preferred
embodiments which follow.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0021]The present inventors have made a study on the improvement of the
life characteristic of multi-layer ceramic capacitor using Cu as an
internal electrode and have found that the Ca/Zr ratio and the content of
Mn, Li, B, and Si of CaZrO3 type dielectric ceramics are
determinative factors for the life to accomplish the invention. Further,
conditions for the Ca/Zr ratio and the Li--B--Si compositional ratio that
the CaZrO3 type dielectric ceramics are densified at 1000° C.
or lower even in a state of suppressing the content of Li and B in order
not to lower the life in view of the use of the Cu internal electrode
have been found.

[0022]When the Ca/Zr ratio in the CaxZrO3 type dielectric
ceramics is defined as in a range of: 1.00≦x≦1.10, the life
characteristics can be improved. The range described above is preferred
since the life characteristic is deteriorated when the value for x is
less than 1.00 or more than 1.10.

[0023]For the Mn content, that is, the value for a, the life
characteristic is improved by defining the range as:
0.5≦a≦4.0 mol based on 100 mol of CaxZrO3. The
range described above is preferred since the life characteristic is
deteriorated when the value for a is less than 0.5 mol or more than 4.0.

[0024]When the total content b+c+d for Li+B+Si is defined as within a
range of: 6.0≦b+c+d≦15.0 mol based on 100 mol of
CaxZrO3, sintering (densification) is possible at 1000°
C. or lower, and the life characteristic is improved. The range described
above is preferred since sintering cannot be conducted at 1000° C.
or lower when b+c+d is less than 6.0 and the life characteristic is
deteriorated when it is more than 15.0 mol.

[0025]When the Li/(B+Si) ratio, b/(c+d) is defined as within a range of
0.15≦b/(c+d)≦0.55, sintering (densification) is possible at
1000° C. or lower. The range described above is preferred since
sintering (densification) is not possible when b/(c+d) is less than 0.15
or more than 0.55.

[0026]When the Si/B ratio, that is, d/c is defined as:
0.20≦d/c≦3.30, sintering (densification) at 1000° C.
or lower is possible and the life characteristic is improved. The range
described above is preferred since the life characteristic is
deteriorated when d/c is less than 0.20 and sintering at 1000° C.
or lower is not possible when it is more than 3.30.

[0027]For optionally designing dielectric characteristics, etc. it is also
possible to substitute a portion of CaxZrO3 as the main
ingredient of the dielectrics by Sr, Ti or the like into
(CaySr1-y)x(ZrzTi1-z)O3 (where
1.00≦x≦1.10, 0<y≦1, 0<z≦1). That is,
(Ca0.9Sr0.1)xZrO3,
Ca(Zr0.9Ti0.1)xO3, etc. can be used as the main
ingredient. Further, for optionally designing the dielectric
characteristic or the like, other elements such as Mg and Al can also be
added together with Mn, Li, B and Si.

[0028]The method of manufacturing the multi-layer ceramic capacitor is not
particularly restricted and the following methods can be adopted. As the
starting material, CaCO3, ZrO2 and, further, optionally,
SrCO3, TiO2, etc. are provided, and the starting materials are
weighed so as to obtain a predetermined composition. Then, after wet
mixing the starting materials and drying them, they were calcined at 800
to 1200° C. to obtain CaxZrO3. For CaxZrO3
synthesized as described above, starting Mn material (oxide, carbonate,
etc.), starting Li material (Li2CO3, etc.), starting B material
(B2O3, etc.) and starting Si material (SiO2, etc.) and,
further optionally, starting Mg material (MgO), starting Al material
(Al2O3), etc. are weighed so as to obtain a predetermined
composition. Then, the starting materials are wet-mixed and dried to
obtain a dielectric powder. A PVB binder (or acryl binder), a
plasticizer, and an organic solvent as a solvent are added properly to
the dielectric powder obtained as described above to prepare a slurry and
a green sheet of a predetermined thickness (5 to 50 μm) is prepared. A
Cu paste for internal electrode was printed, laminated, and press bonded
to the green sheet, and is then cut out into predetermined shape. Then, a
debinding treatment is applied under an inert atmosphere at 300 to
600° C. such that Cu is not oxidized and firing is conducted in a
reducing atmosphere at 900 to 1050° C. for 1 to 5 hours. After
coating a Cu external electrode paste as a terminal electrode to the
obtained sintered body, it is baked in an N2 atmosphere.

[0029]In the present disclosure where conditions and/or structures are not
specified, the skilled artisan in the art can readily provide such
conditions and/or structures in view of the present disclosure, as a
matter of routine experimentation. Further, testing and/or measuring
methods which are not specified in the present disclosure can be any
suitable and/or conventional methods the skilled artisan in the art would
employ.

EXAMPLES

Example 1

[0030]CaCO3 and ZrO2 were provided as starting materials. The
starting materials were weighed and the Ca/Zr ratio, that is, the value
for x was changed in a range from 0.98 to 1.12 as shown in Table 1. Then,
after wet-mixing the starting materials in a ball mill and drying them,
they were calcined at 1000° C. to obtain CaxZrO3
(0.98≦x≦1.12). MnCO3, Li2CO3,
B2O3, and SiO2 were weighed based on the CaxZrO3
(hereinafter simply referred to as CaZrO3), such that the Mn
content, that is, the value a was changed in a range from 0 to 5.0 mol,
the Li/(B+Si) ratio, that is, the value b/(c+d) was changed within a
range from 0.21 to 0.50, the Si/B ratio, that is, the value d/c was
changed in a range from 0.24 to 2.35, and the content b+c+d for the total
of Li+B+Si was changed in a range from 3.0 to 18.0 mol based on 100 mol
of CaZrO3 as shown in Table 1. Then, by wet-mixing the starting
materials in a ball mill and drying them, a dielectric powder was
obtained. A PVB binder, a plasticizer, and an organic solvent as a
solvent were added properly to the dielectric powder to prepare a slurry,
and a green sheet of 12 μm thickness was prepared by a die coater.
After printing a Cu paste for internal electrode by a screen printing
method to the green sheet, and laminating and press-bonding the same by
the number of electrodes of 11 layers (10 inter-layers), they were cut
into 4.0 mm×2.0 mm. Then, a debinding treatment was conducted in an
inert atmosphere at 300 to 600° C. and firing was conducted in a
reducing atmosphere (nitrogen-hydrogen gas mixture: hydrogen ratio 1 to
3%) at 980° C. for 2 hr. Then, a Cu paste was coated as a terminal
electrode and baked in an N2 atmosphere. With the steps as described
above, ten layer multi-layer ceramic capacitors (sample Nos. 101 to 121)
each of 3.2 mm×1.6 mm size were manufactured.

[0031]By using the multi-layer ceramic capacitors described above,
evaluation was conducted on the following characteristics.

(1) For sinterability (densification), samples (10×10×15 mm)
were prepared each by the number of 5 according to the measuring method
of JIS C 2141 separately from the example described above and measured.
Those showing the water absorption of 0.1% or less when fired at
980° C. were evaluated as ".circleincircle.", and others were
evaluated as "x".(2) For the permittivity, each of the samples was
prepared by the number of 20, the static capacitance at 1V-1 MHz was
measured in a circumstance at 20° C. according to JIS C 5102 and
it was determined based on the result of the measurement according to the
following formula.

[0032]Permittivity=(capacitance×thickness of dielectric
layer/(electrode crossing area×number of lamination))/permittivity
of vacuum. The thickness of the dielectrics and the electrode crossing
area were measured by using SEM observation for sample pieces.

(3) TC (static capacitance temperature characteristic) was measured based
on the standards of JIS C 5101-8 (IEC 60384-8). Those showing the change
of coefficient of capacitance within 0±30 (ppm/° C.) in a
temperature range of -55° C. to 125° C. were indicated as
COG assuming the capacitance at 20° C. as a reference.(4)
Reliability: in a high temperature accelerated load test HALT (Highly
Accelerated Life Time) test (condition: 30V/μm, 150° C.), those
showing MTTF of 100 hr or more were evaluated as and those showing less
than 100 hr were evaluated as "x". For sample Nos. 101 to 114, the
composition for dielectrics and evaluation results for the characteristic
of the capacitors are shown in Table 1.

[0033]Since the electric characteristics have no so significant difference
with those of dielectric ceramics in the patent documents described in
the part of the background art, they were omitted and only the basic
characteristic, i.e., temperature characteristic of the permittivity and
the static capacitance were shown.

[0034]As shown in Table 1, the capacitors of the sample Nos. 104 to 107,
and 109 as examples of the present invention having the Ca/Zr ratio, that
is, the value x of from 1.00 to 1.10, the Mn content, that is, the value
a of from 0.5 to 4.0 mol, and the total content b+c+d for Li+B+Si is from
6.0 to 15.0 mol based on 100 mol of CaZrO3 could be sintered
(densified) at 1000° C. or lower and improved for the life as 100
hr or longer. On the contrary, in the capacitors of sample No. 102 with
the Ca/Zr ratio of less than 1.00, and the capacitors of sample Nos. 110,
111 with the Ca/Zr ratio of exceeding 1.10, the life was less than 100
hr. In the capacitor of sample No. 103 not containing Mn and the
capacitor of sample No. 108 with the Mn content exceeding 4.0 mol, the
life was less than 100 hr. Further, the capacitor of sample No. 101 with
the total content b+c+d for Li+B+Si of less than 6.0 mol could not be
sintered (densified) at 1000° C. or lower, and the capacitor with
the total content b+c+d for Li+B+Si exceeding 15.0 mol showed a life of
less than 100 hr.

Example 2

[0035]Dielectric powders were obtained in the same manner as in Example 1
except for mixing while setting the Mn content, that is, the value a to
0.5 or 4.0 mol, the total content b+c+d for Li+B+Si to 6.0 or 15.0 mol,
and changing the Li/(B+Si) ratio, that is, b/(c+d), and the Si/B ratio,
that is, d/c as shown in Table 2 based on 100 mol of CaZrO3 with the
Ca/Zr ratio, that is, the value x of 1.00. Then, sample Nos. 201 to 217
as 10 layer multi-layer ceramic capacitors were manufactured each at a
size of 3.2 mm×1.6 mm in the same manner as in Example 1 and
evaluation was conducted on the characteristics. Table shows the result
of evaluation for the composition of the dielectrics and each of the
characteristics of the capacitors for sample Nos. 201 to 217.

[0036]As shown in Table 2, the capacitors of sample Nos. 201, 202, 204,
205, 211 to 216 of the present invention having the Li/(B+Si) ratio, that
is, b/(c+d) of from 0.15 to 0.55, and the Si/B ratio, that is, d/c of
from 0.20 to 3.30 could be sintered (densified) at 1000° C. or
lower and improved with the life as 100 hr or more. On the contrary, the
capacitors of sample Nos. 203, 206 not containing Li with the Li/(B+Si)
ratio, that is, b/(c+d) of 0 and the capacitors of sample Nos. 208 to 210
with the Li/(B+Si) ratio, that is, b/(c+d) of exceeding 0.55 could not be
sintered (densified) at 1000° C. or lower. Further, the capacitor
of sample No. 207 not containing Si with the Si/B ratio, that is d/c of
0, had a life of less than 100 hr and the capacitor of sample No. 217
with the Si/B ratio, that is, d/c exceeding 3.30 could not be sintered
(densified) at 1000° C. or lower.

Example 3

[0037]Dielectric powders were obtained in the same manner as in Example 1
except for setting Mn to 2.0 mol, the total content b+c+d for Li+B+Si to
12.0 mol, the Li/(B+Si) ratio, that is, b/(c+d) to 0.37 and the Si/B
ratio, that is, d/c at 0.61 (Li: 3.24 mol, B: 5.45 mol, Si: 3.31 mol)
and, further, mixing Mg(MgO) by 1.0 mol, Mg(MgO) by 2.0 mol, and
Al(Al2O3) by 0.5 mol respectively based on 100 mol of
CaZrO3 with the value x for the Ca/Zr ratio at 1.05. Then,
multi-layer ceramic capacitors of sample Nos. 301 to 303 were prepared in
the same manner as in Example 1 and the characteristics were evaluated.
Further, dielectric powders were obtained in the same manner as in
Example 1 except for using (Ca0.9Sr0.1) ZrO3 with a
portion of Ca in CaZrO3 being substituted by Sr, or
Ca(Zr0.9Ti0.1)O3 with a portion of Zr being substituted by
Ti, while setting the Mn content, that is, the value a to 2.0 mol, the
total content b+c+d for Li+B+Si to 12.0 mol, the Li/(B+Si) ratio, that
is, b/(c+d) to 0.37, and the Si/B ratio, that is, d/c to 0.61 (Li: 3.24
mol, B: 5.45 mol, and Si: 3.31 mol) based on 100 mol of
(Ca0.9Sr0.1)ZrO3 or Ca(Zr0.9Ti0.1)O3 with
the (Ca+Sr)/Zr ratio or the Ca/(Zr+Ti) ratio, that is, the A/B ratio of
1.05. Then, multi-layer ceramic capacitors of sample Nos. 304 and 305
were prepared and the characteristics were evaluated in the same manner
as in Example 1.

[0038]As shown in Table 3, in a case of substituting a portion of Ca with
Sr or substituting a portion of Zr with Ti in CaZrO3, even when
other ingredients than Mn, Li, B, and Si such as Mg, Al, etc. are
contained, multi-layer ceramic capacitors that could be sintered
(dencified) at 1000° C. or lower and had a life of 100 hr or more
could be obtained by defining the Ca/Zr ratio (A/B ratio) as 1.00 to
1.10, and the Mn content, that is, the value a as 0.5 to 4.0 mol, and the
total content b+c+d for Li+B+Si as 6.0 to 15.0 mol, the Li(B+Si) ratio,
that is, b/(c+d) as 0.15 to 0.55, and the Si/B ratio, that is, d/c as
0.20 to 3.30 based on 100 mol of CaZrO3.

[0039]The compositions of the dielectric ceramics of the invention are not
restricted to the descriptions described above but various modifications
are possible within a range not departing the gist of the invention. For
example, simultaneous substitution for the portion of Ca in the
CaxZrO3 as the main ingredient by two elements Ti and Sr has
been conducted generally, which is also within a range of the purpose of
the invention and is permitted. Further, simultaneously with partial
substitution for Ca, addition of Mg and Al alone or simultaneously for
the two ingredients is also within the range of the purpose of the
invention and is permitted.

[0040]Therefore, it should be clearly understood that the forms of the
present invention are illustrative only and are not intended to limit the
scope of the present invention.

[0041]The present application claims priority to Japanese Patent
Application No. 2007-171337, filed Jun. 29, 2007, the disclosure of which
is incorporated herein by reference in its entirety.